CN101851161A - Large molecular weight polyalcohol and polyprotic acid organic ester and synthesis method and application thereof - Google Patents
Large molecular weight polyalcohol and polyprotic acid organic ester and synthesis method and application thereof Download PDFInfo
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Abstract
The invention relates to large molecular weight polyalcohol and polyprotic acid organic ester, named 2-monohydric alcohol diacid carbonic acid polyalcohol-dibasic acid ester. The large molecular weight polyalcohol and polyprotic acid organic ester has a structural formula shown as the specification, wherein a monohydric alcohol group is an n-octyl alcohol group, an isooctanol group, an n-butyl alcohol group or an isobutanol group; a diacid group is an adipic acid group or a sebacic acid group; a medium carbonic acid group is an isocaprylic acid group, an octanoic acid group or a capric acid group; and a polyalcohol group is a Di-Penta group. The large molecular weight polyalcohol and polyprotic acid organic ester has the advantages of large molecular weight, favorable compatibility and antistatic property, weak water absorbability and the like.
Description
Technical field
The technology of the present invention belongs to the fine chemical technology field, relates to a kind of macromolecule organosilane ester product, the stablizer major function raw material that uses in particularly a kind of plastic working and synthetic method and purposes.
Background technology
The thermo-stabilizer that plastics (PVC) processing is used mainly contains traditionally: lead salt or cadmium salt class, organo-metallic soap class, organic tin, one package stabilizer class etc.Though lead salt or cadmium salt class stablizer have good thermal stability, toxicity is sympathized victimization body health greatly.The thermal stability of nontoxic organo-metallic soap class stablizer can't with lead salts or cadmium salt analogy.The organic tin stablizer is highly effective thermo-stabilizer, can make transparent article keep very high transparency, and consumption is less, but it costs an arm and a leg, and peculiar smell is arranged, unlubricated property.Organotin is harmful to human central nervous simultaneously.Though one package stabilizer occurs at the product that does not also have at present can replace fully as organotin, this class stablizer can be optimized the advantage of various stablizers, learns from other's strong points to offset one's weaknesses, the product that produces.
One package stabilizer is many with calcium/zinc composite stabilizer, based on calcium/zinc salt, also comprises organic auxiliary stabilizer, oxidation inhibitor and lubricant in the system, and stability and the processing characteristics of PVC had material impact.Exploitation calcium/zinc composite stabilizer, how research brings into play the synergy of each component, and development efficient and environment-friendly type stablizer has vital role to promoting PVC traditional industry upgrading and development.
Stable mechanism is realized by following several respects.1. by catching the HCl that the PVC thermolysis produces, prevent the catalyzed degradation effect of HCl.2. replace active chlorallylene atom.3. and free radical reaction, stop the reaction of free radical.4. with the conjugated double bond addition, suppress the growth of gripping chain altogether.5. decompose hydroperoxide reduces the number of free radical.6. passivation has catalysis to take off the metal ion of HCl effect.One package stabilizer can be accomplished to realize the heat-staple purpose of PVC by above-mentioned several different mechanism simultaneously.This also is a big advantage of one package stabilizer.
The material performance of calcium/zinc stabilizer, as calcium stearate (CaSt), good processability has lubrication, and no sulfide staining is nontoxic, but thermostability is lower, and transparency is bad.Zinic stearas (ZnSt), nontoxic and transparent, after consumption is big, cause easily that " zinc burning " causes the goods blackening.In principle, calcium and zinc salt form the structure of calcium/zinc complexes in the blend process, unstable chlorine atomic reaction on Ca/Zn mixture and the PVC molecular chain, having suppressed PVC advances one and relates to and decompose to discharge HCI, thereby static stabilization has been played in the thermolysis to PVC, adds simultaneously polyvalent alcohol, organotin, zeolite, phosphorous acid ester, beta-diketon etc. in the Ca/Zn mixture PVC stable had the obvious synergistic effect.One package stabilizer as Ca/Zn and organotin shows: organotin and Ca/Zn are compound, have not only improved the color stability of polyvinyl chloride resin, and have improved its thermostability.Make it have good thermostability and processing characteristics.But organotin, phosphorous acid ester, beta-diketon etc. all contain the composition of heavy metal or benzene, and be harmful to human central nervous, is still unsafe.
Summary of the invention
The objective of the invention is to provide a kind of interpolation compound that can replace organotin, phosphorous acid ester, beta-diketon etc. compound with calcium/zinc for the deficiency that solves above-mentioned technology, stability is good, no zinc burns, macromolecule polyvalent alcohol polyprotonic acid organic ester and the synthetic method and the purposes of asepsis environment-protecting.
In order to achieve the above object, the macromolecule polyvalent alcohol polyprotonic acid organic ester that the present invention is designed, its title is: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four.Its structural formula is:
Wherein the monohydroxy-alcohol group is that n-Octanol group or isooctyl alcohol group or propyl carbinol group or isopropylcarbinol group arrive; Described diacid groups is hexanodioic acid group or sebacic acid group; The carbonic acid group is isocaprylic acid group or n-caprylic acid group or n-capric acid group in described; Described polyvalent alcohol group is the dipentaerythritol group.
Further, this macromolecule polyvalent alcohol polyprotonic acid organic ester can be two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, and its structural formula is:
In the formula:
Octanol hexanodioic acid ester group---(CH
3(CH
2)
6CH
2O
2C (CH
2)
4CO
2)-
Four isocaprylic acid dipentaerythritol ester groups---
-(CH
2(CH
2CO
2(CH
2)
6CH
3)
2C-CH
2OCH
2-C (CH
2CO
2(CH
2)
6CH
3)
2CH
2)-hexanodioic acid base----O
2C (CH
2)
4CO
2-
Its molecular structural formula is:
Molecular weight is: 2106.
The resulting macromolecule polyvalent alcohol of the present invention polyprotonic acid organic ester, characteristics such as it is big to have a molecular weight, and consistency and static resistance are preferably arranged, and water-absorbent is weak.Wherein said monohydroxy-alcohol group plays the effect that improves this organic ester consistency at the two ends of molecular structure; Described diacid groups plays in molecular structural formula and connects monohydroxy-alcohol group and polyvalent alcohol group, and the effect that connects two polyvalent alcohol groups; Described polyvalent alcohol group plays the raising molecular weight, increases the effect of the stability of this organic ester; The carbonic acid group is connected with the polyvalent alcohol group in described, plays the hydroxyl that reduces in the macromolecular polyol ester, improves the water-absorbent of polyvalent alcohol polyprotonic acid organic ester, further increases the effect of the consistency of macromole organic ester.
The resulting macromolecule polyvalent alcohol of the present invention polyprotonic acid organic ester is a best results with two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters again.Two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters can reach the highest cost performance.
The synthetic method of the macromolecule polyvalent alcohol polyprotonic acid organic ester of the present invention design i.e. the synthetic method of two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, is that to be divided into for four steps synthetic:
The first step is that the esterification of octanol adipic acid ester is synthetic, its chemical equation:
CH
3(CH
2)
6CH
2OH+HO
2C(CH
2)
4CO
2H-→CH
3(CH
2)
6CH
2CO
2(CH
2)
4CO
2H+H
2O
The reaction process of the first step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in n-Octanol and hexanodioic acid proportioning adding in 1: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 100-140 ℃, reaction times 180-260 minute, cooling after constant temperature oven insulation filter the octanol adipic acid ester;
Second step was the synthetic of four isocaprylic acid bis(pentaerythritolester)s, its chemical equation:
The reaction process in second step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in isocaprylic acid and dipentaerythritol proportioning adding in 4: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 130-180 ℃, reaction times 200-260 minute, get four isocaprylic acid bis(pentaerythritolester)s;
The 3rd step was the synthetic of two dipentaerythritol, four isocaprylic acid adipic acid esters, its chemical equation:
The reaction process in the 3rd step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in four isocaprylic acid bis(pentaerythritolester)s and hexanodioic acid proportioning adding in 2: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 130-200 ℃, reaction times 180-240 minute, cooling after constant temperature insulation filter two dipentaerythritol, four isocaprylic acid adipic acid esters;
The 4th step was the synthetic of two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, and its chemical equation is:
The reaction process in the 4th step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in two dipentaerythritol, four isocaprylic acid adipic acid esters and octanol adipic acid ester proportioning adding in 1: the 2 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 160-210 ℃, reaction times 180-240 minute, through constant temperature oven insulation filter polyvalent alcohol organic acid organic ester---two-octanol hexanodioic acid, the four isocaprylic acid dipentaerythritol-adipic acid esters of macromolecule.
Wherein, the catalyzer that uses in described four step synthetic methods is: nontoxic metal oxide and inorganic salt and organic metal salt any one or two kinds of mixing are composite; When two kinds of catalyzer are composite, all by 1: 1 mixed.Composite as any one or two kinds of mixing in iron trichloride, tin protochloride, sodium pyrosulfate, zinc oxide, Tai-Ace S 150, sodium pyrosulfate, titanium oxide, the tetrabutyl titanate.
The purposes of macromolecule polyvalent alcohol polyprotonic acid organic ester of the present invention is that macromolecule polyvalent alcohol polyprotonic acid organic ester and calcium/zinc soap are re-dubbed PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer.According to different needs, can (as calcium soap: zinc soap: macromolecule polyvalent alcohol organic ester 1: 2: 1) proportioning be carried out compositely, obtains multiple PVC calcium such as solid or pasty state or transparent liquid etc./zinc polyvalent alcohol organosilane ester thermo-stabilizer by different mol ratios.
Of the present invention with macromolecule polyvalent alcohol polyprotonic acid organic ester and the composite purposes that obtains stablizer of calcium/zinc soap, good effect is arranged.Synergistic effect when we have tested polyvalent alcohol polyprotonic acid organic ester and calcium/soap as the PVC stablizer.
Test shows:
1. the sour organic ester of macromolecule polyvalent alcohol unit shows good dispersiveness in PVC, and stabilising effect is better than using micromolecular polyol ester.
2. macromolecule polyvalent alcohol polyprotonic acid organic ester is a kind of important polyvinyl chloride (PVC) auxiliary heat stabilizer, and metal soap thermal stabilizers such as it and calcium/zinc and with improving " zinc burning " phenomenon is significantly obtained the good long term thermostable effect.
Inserted consistency group ester group on our hydroxyl in macromolecule polyvalent alcohol polybasic ester molecule, as isocaprylic acid (or n-caprylic acid) to reduce the hydroxyl in the molecule, consistency and static resistance have been improved with PVC, can improve the raising transparency of products, itself and calcium/zinc metal soap thermal stabilizers is composite.
Test shows introduces consistency group ester group in macromolecular polyol polyprotonic acid organic ester molecule, composite with calcium/zinc metal soap thermal stabilizers, obviously increase with the consistency of polyvinyl chloride resin, outstanding behaviours is to promote the transparency of product to increase, improve the water-absorbent that has reduced product simultaneously, its initial stage and long-term auxiliary heat stability are significantly better than other polyol ester, and its reason is that good consistency has increased dispersiveness, thereby has increased thermostability.Because this product is the macromole esters product, thereby not only has consistency, and also has good lubricity.This product all is better than phosphorous acid ester and epoxy compounds type thermal stabilizing agent as the auxiliary heat stabilising effect of calcium/zinc metal soap thermal stabilizers.The lead salts thermo-stabilizer that its initial stage thermostability is better than using always, near organo-tin het stabilizer, its long-term thermal stability can also be better than organotin and lead salts stablizer, and this type thermal stabilizing agent is nontoxic.Therefore the composite thermo-stabilizer of this product and calcium/zinc soap can replace calcium/zinc-organotin compound thermo-stabilizer.
In macromolecular polyol polyprotonic acid organic ester molecule, introduce the consistency group, composite with calcium/zinc metal soap thermal stabilizers, make novel PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer.Can reach nontoxic, pollution-free, compound and function efficiently, also be a kind of trial of innovation in its PVC calcium/zinc composite heat stabilizer field, and its superior performance can cause very big repercussion, has vital role to promoting PVC traditional industry upgrading and development.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1:
The macromolecule polyvalent alcohol polyprotonic acid organic ester that present embodiment is described, it is: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four.Its molecular structure is:
It is two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, and its concrete structural formula is:
In the formula:
Octanol hexanodioic acid ester group---(CH
3(CH
2)
6CH
2O
2C (CH
2)
4CO
2)-
Four isocaprylic acid dipentaerythritol ester groups---
-(CH
2(CH
2CO
2(CH
2)
6CH
3)
2C-CH
2OCH
2-C (CH
2CO
2(CH
2)
6CH
3)
2CH
2)-hexanodioic acid base----O
2C (CH
2)
4CO
2-
Its concrete molecular structural formula is:
Molecular weight is: 2106.
The synthetic method of two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters is that to be divided into for four steps synthetic:
The first step is that the esterification of octanol adipic acid ester is synthetic, its chemical equation:
CH
3(CH
2)
6CH
2OH+HO
2C(CH
2)
4CO
2H-→CH
3(CH
2)
6CH
2CO
2(CH
2)
4CO
2H+H
2O
The reaction process of the first step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in n-Octanol and hexanodioic acid proportioning adding in 1: the 1 in molar ratio reaction flask, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 100-140 ℃, reaction times 180-260 minute, cooling after constant temperature oven insulation filter the octanol adipic acid ester;
Second step was the synthetic of four isocaprylic acid bis(pentaerythritolester)s, its chemical equation:
The reaction process in second step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in isocaprylic acid and dipentaerythritol proportioning adding in 4: the 1 in molar ratio reaction flask, catalyzer is the compound of pyroprocessing Tai-Ace S 150 and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-180 ℃, reaction times 200-260 minute, get four isocaprylic acid bis(pentaerythritolester)s;
The 3rd step was the synthetic of two dipentaerythritol, four isocaprylic acid adipic acid esters, its chemical equation:
The reaction process in the 3rd step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in four isocaprylic acid bis(pentaerythritolester)s and hexanodioic acid proportioning adding in 2: the 1 in molar ratio reaction flask, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-200 ℃, reaction times 180-240 minute, cooling after constant temperature insulation filter two dipentaerythritol, four isocaprylic acid adipic acid esters;
The 4th step was the synthetic of two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, and its chemical equation is:
The reaction process in the 4th step is: electronic stirring is being housed, electrically heated, reflux exchanger, in the reaction flask of temp measuring system, to carry out esterification in two dipentaerythritol, four isocaprylic acid adipic acid esters and octanol adipic acid ester proportioning adding in 1: the 2 in molar ratio reaction flask, the compound of catalyst oxidation zinc and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 160-210 ℃, reaction times 180-240 minute, through constant temperature oven insulation filter polyvalent alcohol polyprotonic acid organic ester---two-octanol hexanodioic acid, the four isocaprylic acid dipentaerythritol-adipic acid esters of macromolecule.
The method that this two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters and calcium/zinc soap is re-dubbed PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer is:
Get calcium stearate 250g, Zinic stearas 375g, two-octanol hexanodioic acid, the four isocaprylic acids dipentaerythritol-adipic acid ester 375g of macromolecule carries out compositely, makes the powder composite thermal stabilizer of PVC calcium/zinc polyvalent alcohol organosilane ester.
Two-octanol hexanodioic acid, four isocaprylic acids dipentaerythritol-adipic acid ester application test situation:
At this two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters are abbreviated as:
The macromole ester
1. specimen preparation
Table 1. test recipe
| Prescription | ??1# | ??2# | ??3# | ??4# | ??5# |
| The polyvinyl chloride resin powder | ??100 | ??100 | ??100 | ??100 | ??100 |
| Calcium stearate | ? | ??1.0 | ? | ??1.5 | ? |
| Zinic stearas | ? | ??1.5 | ? | ??1.5 | ? |
| Calcium iso-octoate | ? | ? | ??1.25 | ? | ? |
| Isocaprylic acid zinc | ? | ? | ??1.25 | ? | ? |
| The macromole ester | ? | ??1.5 | ??1.5 | ? | ? |
| The triphenyl phosphorous acid ester | ? | ? | ? | ??1.0 | ? |
| The TM181 methyl tin stabilizer | ? | ? | ? | ? | ??1.5 |
| Lead stearate | ??0.5 | ? | ? | ? | ? |
| Lead sulfate tribasic | ??3.5 | ? | ? | ? | ? |
Pressing the prescription in the table 1, after material is mixed with high-speed mixer, is about 9min that plasticates on the double roller plastic-making device of 1-2mm at 180-190 ℃, roll spacing, gets sheet after the plasticizing fully.
2 performance tests
2.1. dynamic thermal stability energy and processing rheological property
The temperature of setting the rheometer Banbury mixer is that 180 ℃, rotating speed are that 30r/min, load are 5kg, and various raw materials are mixed by the proportioning in the table 1, adds rheometer then and carries out banburying.The floating weight of Banbury mixer is opened in the plasticizing back, observes the material colour-change under the condition of opening.Obtain processing characteristics parameters such as the balancing torque of material and gel time from moment of torsion-time curve simultaneously.
2.2. static heat stability
To sample be cut into identical little side's sheet after the test, sample strip is put into rotation senile experiment case, carry out weathering test at 180 ℃, every sampling in 5-10 minute once, the aging sample sheet is measured colour-change with colourimeter.
3 Try Examination results
3.1 dynamic thermal stability Qing Condition:
The various prescription of table 2 PVC banburying variable color time in rheometer
| Prescription | Initial coloration time/minute | Blackout time/minute | The transparency |
| ??2# | ??13.30 | ??19.30 | Very |
| ??3# | ??13.10 | ??19.10 | Very |
| ??4# | ??10.40 | ??16.30 | Difference |
| ??5# | ??13.40 | ??19.20 | Very |
Table 2 shows that the consistency of macromole ester and polyvinyl chloride resin is good, and its initial stage and long-term auxiliary heat stability are all significantly better than the triphenyl phosphorous acid ester.Basic identical with methyl tin stabilizer.
3.2 processing rheological property Qing Condition:
The rheological property of the different stabilising system PVC of table 3
| The prescription sample number into spectrum | Minimum value torque value/Nm | Maximum value torque value/Nm | End value torque value/Nm | Gel time/s |
| ??1# | ??9.8 | ??45.6 | ??40.6 | ??496 |
| ??2# | ??8.9 | ??43.4 | ??41.8 | ??490 |
[0091]
| ??5# | ??9.6 | ??43.2 | ??40.2 | ??492 |
Table 3 shows that the lead salts thermo-stabilizer is all more similar to methyl tin stabilizer with macromole ester calcium zinc heat stabilizer, has lower maximum rotation torque value (45-43Nm) and grows the gelation time of (greater than 490s).Gelation time is also identical.
3.3 static heat stability Qing Condition:
The static heat stability of the different stabilising system PVC of table 4
Table 4 shows that two macromole ester auxiliary heat stabilising effects all are better than the phosphorous acid ester type thermal stabilizing agent.The lead salts thermo-stabilizer that the initial stage thermostability is better than using always, near organo-tin het stabilizer, long-term thermal stability is better than organotin and lead salts stablizer, and the composite calcium/zinc composite heat stabilizer of this product is nontoxic, is to can be used as to substitute existing organo-tin het stabilizer and the good product of calcium zinc type thermal stabilizing agent.
Embodiment 2:
The macromolecule polyvalent alcohol polyprotonic acid organic ester that present embodiment is described, its molecular structure is: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four.It is two-octanol sebacic acid, four isocaprylic acid dipentaerythritol-sebates.Its concrete molecular structure is:
Its concrete synthetic method is:
Step 1: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with n-Octanol 130g, sebacic acid 202g, add in the reaction flask and carry out esterification, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 100-160 ℃, reaction times 180-260 minute, cooling after constant temperature oven insulation filter the octanol sebate.
Step 2: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with isocaprylic acid 632g, dipentaerythritol 254g, add in the reaction flask and carry out esterification, catalyzer is the compound of pyroprocessing Tai-Ace S 150 and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-180 ℃, reaction times 200-260 minute, get four isocaprylic acid bis(pentaerythritolester)s.
Step 3: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with four isocaprylic acid bis(pentaerythritolester) 162.8g, sebacic acid 20.2g, add in the reaction flask and carry out esterification, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-200 ℃, reaction times 180-240 minute, cooling after constant temperature oven insulation filter two dipentaerythritol, four isocaprylic acid sebates.
Step 4: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with two dipentaerythritol, four isocaprylic acid sebate 179.4g, octanol sebate 62.8g, add in the reaction flask and carry out esterification, the compound of catalyst oxidation zinc and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 160-210 ℃, reaction times 180-240 minute, through constant temperature oven insulation filter polyvalent alcohol organic acid organic ester---two-isooctyl alcohol sebacic acid, the four isocaprylic acid dipentaerythritol-sebates of macromolecule.
The method that this two-octanol sebacic acid, four isocaprylic acid dipentaerythritol-sebates and calcium/zinc soap is re-dubbed PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer is: get calcium stearate 250g, Zinic stearas 400g, two-octanol sebacic acid, the four isocaprylic acids dipentaerythritol-sebate 300g of macromolecule, triglycol two 2-ethylhexoate 50g, carry out compositely, make the powder composite thermal stabilizer of PVC calcium/zinc polyvalent alcohol organosilane ester.
Embodiment 3
The macromolecule polyvalent alcohol polyprotonic acid organic ester that present embodiment is described, its molecular structure is: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four.It is two-isooctyl alcohol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters.
Its concrete molecular structure is:
Its concrete synthetic method is:
Step 1: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with isooctyl alcohol 130g, hexanodioic acid 146g, add in the reaction flask and carry out esterification, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 100-160 ℃, reaction times 180-260 minute, cooling after constant temperature oven insulation filter the isooctyl alcohol sebate.
Step 2: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with isocaprylic acid 632g, dipentaerythritol 254g, add in the reaction flask and carry out esterification, catalyzer is the compound of pyroprocessing Tai-Ace S 150 and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-180 ℃, reaction times 200-260 minute, get four isocaprylic acid bis(pentaerythritolester)s.
Step 3: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with four isocaprylic acid bis(pentaerythritolester) 162.8g, hexanodioic acid 14.6g, add in the reaction flask and carry out esterification, catalyzer is the compound of zinc oxide and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 130-200 ℃, reaction times 180-240 minute, cooling after constant temperature oven insulation filter two dipentaerythritol, four isocaprylic acid adipic acid esters.
Step 4: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, with two dipentaerythritol, four isocaprylic acid adipic acid ester 179.4g, isooctyl alcohol adipic acid ester 51.6g, add in the reaction flask and carry out esterification, the compound of catalyst oxidation zinc and tetrabutyl titanate, catalyst levels 0.3-1.0%, temperature of reaction 160-210 ℃, reaction times 180-240 minute, through constant temperature oven insulation filter polyvalent alcohol organic acid organic ester---two-isooctyl alcohol hexanodioic acid, the four isocaprylic acid dipentaerythritol-adipic acid esters of macromolecule.
The method that this two-isooctyl alcohol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters and calcium/zinc soap is re-dubbed PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer is: get calcium stearate 250g, Zinic stearas 400g, two-isooctyl alcohol hexanodioic acid, the four isocaprylic acids dipentaerythritol-adipic acid ester 300g of macromolecule, triglycol two 2-ethylhexoate 50g, carry out compositely, make the powder composite thermal stabilizer of PVC calcium/zinc polyvalent alcohol organosilane ester.
Embodiment 4
Two-octanol hexanodioic acid that embodiment 1 is obtained, four isocaprylic acid dipentaerythritol-adipic acid esters that present embodiment is described are as synthetic preparation PVC calcium/zinc polyvalent alcohol organosilane ester transparent liquid composite thermal stabilizer.Its concrete method is: get calcium iso-octoate 300g, isocaprylic acid zinc 300g, two-octanol hexanodioic acid, the four isocaprylic acids dipentaerythritol-adipic acid ester 300g of the macromolecule that embodiment 1 produces, epoxy soybean oil 50g, triglycol two 2-ethylhexoate 50g, carry out compositely, make PVC calcium/zinc polyvalent alcohol organosilane ester transparent liquid composite thermal stabilizer.
Embodiment 5
Two-octanol hexanodioic acid that embodiment 1 is obtained, four isocaprylic acid dipentaerythritol-adipic acid esters that present embodiment is described are as synthetic preparation PVC unsymmetric structure calcium/zinc polyvalent alcohol organosilane ester powder-type composite thermal stabilizer.Its concrete method is: the calcium stearate 250g that gets unsymmetric structure, Zinic stearas 350g, two-octanol hexanodioic acid, the four isocaprylic acids dipentaerythritol-adipic acid ester 300g of the macromolecule that embodiment 1 produces, epoxy soybean oil 50g, triglycol two 2-ethylhexoate 50g, carry out compositely, make PVC calcium/zinc polyvalent alcohol organosilane ester powder-type composite thermal stabilizer.
Embodiment 6
The macromolecule polyvalent alcohol polyprotonic acid organic ester that present embodiment is described, its molecular structure is: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four.It is two-octanol hexanodioic acid, four n-caprylic acid dipentaerythritol-adipic acid esters, and its concrete molecular structure is:
Also can be two-isooctyl alcohol sebacic acid, four isocaprylic acid dipentaerythritol-sebates, its concrete molecular structure be:
Claims (6)
1. macromolecule polyvalent alcohol polyprotonic acid organic ester is characterized in that its name is called: carbonic acid polyvalent alcohol-diester in two-monohydroxy-alcohol diprotic acid four, and its structural formula is:
2. macromolecule polyvalent alcohol polyprotonic acid organic ester according to claim 1 is characterized in that described monohydroxy-alcohol group is n-Octanol group or isooctyl alcohol group or propyl carbinol group or isopropylcarbinol group; Described diacid groups is hexanodioic acid group or sebacic acid group; The carbonic acid group is isocaprylic acid group or n-caprylic acid group or n-capric acid group in described; Described polyvalent alcohol group is the dipentaerythritol group.
3. macromolecule polyvalent alcohol polyprotonic acid organic ester according to claim 1 is characterized in that title two-octanol hexanodioic acid four isocaprylic acid dipentaerythritol-adipic acid esters, and its molecular structural formula is:
Molecular weight is: 2106.
4. the synthetic method of macromolecule polyvalent alcohol polyprotonic acid organic ester as claimed in claim 3, it is synthetic to it is characterized in that being divided into for four steps: the first step is that the esterification of octanol adipic acid ester is synthetic, its chemical equation:
CH
3(CH
2)
6CH
2OH+HO
2C(CH
2)
4CO
2H→CH
3(CH
2)
6CH
2CO
2(CH
2)
4CO
2H+H
2O
The reaction process of the first step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in n-Octanol and hexanodioic acid proportioning adding in 1: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 100-140 ℃, reaction times 180-260 minute, cooling after constant temperature oven insulation filter the octanol adipic acid ester;
Second step was the synthetic of four isocaprylic acid bis(pentaerythritolester)s, its chemical equation:
The reaction process in second step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in isocaprylic acid and dipentaerythritol proportioning adding in 4: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 130-180 ℃, reaction times 200-260 minute, get four isocaprylic acid bis(pentaerythritolester)s;
The 3rd step was the synthetic of two dipentaerythritol, four isocaprylic acid adipic acid esters, its chemical equation:
The reaction process in the 3rd step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in four isocaprylic acid bis(pentaerythritolester)s and hexanodioic acid proportioning adding in 2: the 1 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 90-120 ℃, reaction times 180-240 minute, cooling after constant temperature insulation filter two dipentaerythritol, four isocaprylic acid adipic acid esters;
The 4th step was the synthetic of two-octanol hexanodioic acid, four isocaprylic acid dipentaerythritol-adipic acid esters, and its chemical equation is:
The reaction process in the 4th step is: in the reaction flask that electronic stirring, electrically heated, reflux exchanger, temp measuring system are housed, to carry out esterification in two dipentaerythritol, four isocaprylic acid adipic acid esters and octanol adipic acid ester proportioning adding in 1: the 2 in molar ratio reaction flask, catalyst levels 0.3-1.0%, temperature of reaction 160-210 ℃, reaction times 180-240 minute, through constant temperature oven insulation filter polyvalent alcohol organic acid organic ester---two-octanol hexanodioic acid, the four isocaprylic acid dipentaerythritol-adipic acid esters of macromolecule.
5. the synthetic method of macromolecule polyvalent alcohol polyprotonic acid organic ester according to claim 4 is characterized in that the catalyzer that uses in described four step synthetic methods is: nontoxic metal oxide and inorganic salt and organic metal salt any one or two kinds of mixing are composite; Two kinds of catalyzer are composite all by 1: 1 mixed.
6. the purposes of macromolecule polyvalent alcohol polyprotonic acid organic ester according to claim 3 is that macromolecule polyvalent alcohol polyprotonic acid organic ester and calcium/zinc soap are re-dubbed PVC calcium/zinc polyvalent alcohol organosilane ester thermo-stabilizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102417453A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Method for preparing citric acid ester |
| CN103570973A (en) * | 2013-10-30 | 2014-02-12 | 芜湖海螺型材科技股份有限公司 | High-speed extruded calcium-zinc compound stabilizer |
| CN107586398A (en) * | 2017-09-27 | 2018-01-16 | 浙江锦润生物科技有限公司 | A kind of colorless and odorless liquid plasticses lubricant and synthetic method |
| CN107722052A (en) * | 2017-09-27 | 2018-02-23 | 杭州金诚助剂有限公司 | One kind contains phosphorous acid organic ester antioxidant and synthetic method |
| CN110407692A (en) * | 2019-08-05 | 2019-11-05 | 嘉兴中诚环保科技股份有限公司 | The synthetic method of the tertiary decylate of polyadipate glycerine |
| CN114409534A (en) * | 2021-12-29 | 2022-04-29 | 广东科力新材料有限公司 | Pentaerythritol ester and preparation method thereof |
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| CN1740225A (en) * | 2005-09-02 | 2006-03-01 | 广东联塑科技实业有限公司 | Epoxy-zinc soap compound as heat stabilizer for compounding polyvinyl chloride plastic |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417453A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Method for preparing citric acid ester |
| CN102417453B (en) * | 2011-12-16 | 2014-04-02 | 中粮生物化学（安徽）股份有限公司 | Method for preparing citric acid ester |
| CN103570973A (en) * | 2013-10-30 | 2014-02-12 | 芜湖海螺型材科技股份有限公司 | High-speed extruded calcium-zinc compound stabilizer |
| CN103570973B (en) * | 2013-10-30 | 2015-01-21 | 芜湖海螺型材科技股份有限公司 | High-speed extruded calcium-zinc compound stabilizer |
| CN107586398A (en) * | 2017-09-27 | 2018-01-16 | 浙江锦润生物科技有限公司 | A kind of colorless and odorless liquid plasticses lubricant and synthetic method |
| CN107722052A (en) * | 2017-09-27 | 2018-02-23 | 杭州金诚助剂有限公司 | One kind contains phosphorous acid organic ester antioxidant and synthetic method |
| CN107722052B (en) * | 2017-09-27 | 2021-03-02 | 杭州金诚助剂有限公司 | Antioxidant containing organic phosphite ester and synthesis method thereof |
| CN110407692A (en) * | 2019-08-05 | 2019-11-05 | 嘉兴中诚环保科技股份有限公司 | The synthetic method of the tertiary decylate of polyadipate glycerine |
| CN114409534A (en) * | 2021-12-29 | 2022-04-29 | 广东科力新材料有限公司 | Pentaerythritol ester and preparation method thereof |
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|---|---|
| CN101851161B (en) | 2013-07-17 |
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